The Rare Earths: Their Occurrence, Chemistry, and Technology — John Shaqi
The Rare Earths: Their Occurrence, Chemistry, and TechnologyLevy, Stanley Isaac
Science
The Rare Earths: Their Occurrence, Chemistry, and Technology
Levy, Stanley Isaac
Rare earths
It appears unlikely that any one explanation can cover all these
interesting facts; there are in each case peculiar factors to be taken
into account. In 1841, Regnault,[36] considering the case of the oxides
observed by Berzelius, inferred that the development of light and heat
denoted that the bodies possessed a lower specific heat after the change
than before. The experimental difficulties encountered in attempting to
dry the oxides prevented him from confirming this view. He measured the
specific heats of the minerals calcite and aragonite (CaCO₃), and of the
two allotropic modifications of phosphorus, but could observe no
appreciable differences. H. Rose (_vide supra_) showed by experiment
that considerable heat was evolved on the glowing of gadolinite, with a
decrease of about one-fourteenth in the specific heat. In the case of
samarskite there was, however, no appreciable evolution of heat, nor
could he determine any difference in the specific heats before and after
glowing.
[36] _Pogg. Ann._ 1841, ~53~, 249.
Probably the only inference that can be safely drawn is that in most
cases the change is due to some molecular re-arrangement. The evolution
of water, helium, etc., in some cases, may possibly be due to
intramolecular change, but on the one hand the current view at present
is that the helium is mechanically held in radio-active minerals, and on
the other hand it is not known that the water evolved is water of
constitution; in an intermolecular change at fairly high temperature,
these might be evolved without disruption of the true mineral molecules.
The question of the energy involved, and consequently of the specific
heats, appears to depend on factors peculiar to each case, of which at
present no accurate conception can be formed; and the change in specific
gravity is probably bound up with these. The loss of solubility in acids
is a factor not always connected with glowing, as it is frequently
observed in the laboratory after ignition of compounds, but here again
no adequate explanation is forthcoming.
The possibility of chemical change in one or two cases, however, must
not be ignored. Thus ammonium magnesium phosphate, NH₄MgPO₄, on heating
glows, and is converted to magnesium pyrophosphate, according to the
equation:
2NH₄MgPO₄ = Mg₂P₂O₇ + H₂O + 2NH₃
A case possibly analogous to this is that of the mineral sipylite
(_q.v._), R´´´₂Cb₂O₈, with ‘basic water’ (_i.e._ R´´´ partially replaced
by H). Before the blowpipe this decrepitates with loss of water, and
glows brilliantly. The specific gravity after the change does not appear
to have been determined. Mallet explains the glow as due to a change to
the pyrocolumbate.
Similar explanations may possibly hold in the cases of allanite and
risörite, but it must be remembered that we are really ignorant of the
part played by the water in these minerals.
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